Phosphate and thiophosphate urethanes



United States Patent 3,220,961 PI-IUSPHATE AND THIGPHQSPHATE URETHANESLester Friedman, Beechwood Village, flhio, assignor to Weston ChemicalCorporation, Newark, N..I., a corporation of New Jersey No Drawing.@riginal application May 28, 1964, Ser. No. 371,122. Divided and thisapplication Dec. 30, 1964, Ser. No. 422,440 ihe portion of the term ofthe patent subsequent to .luly 23, 1981, has been disclaimed 11 Uairns.(til. 2602.)

This application is a division of application Serial No. 371,122, filedMay 28, 1964, which application is a continuation-in-part of applicationSerial No. 129,529, filed August 7, 1961 now Patent No. 3,081,331, andof application Serial No; 145,749, filed October 17, 1961, now PatentNo. 3,142,651.

The present invention relates to the preparation of polyurethanes,including foamed polyurethanes, from phosphite esters containingavailable hydroxyl groups, preferably secondary hydroxyl groups. It alsoincludes the preparation of polyurethanes from the correspondingthiophosphate esters and phosphate esters.

It is an object of the present invention to prepare polyurethanes fromphosphites having at least three free hydroxyl groups.

Another object is to prepare polyurethanes from thiophosphates having atleast three free hydroxyl groups.

A further object is to prepare polyurethanes from phosphites having atleast three free secondary hydroxyl groups.

An additional object is to prepare novel flame-resistant polyurethanes.

A further object is to prepare polyurethanes from hydroxy containingpentaerythritol phosphites.

Yet another object is to prepare improved foamed polyurethanes.

A still further object is to prepare stabilized polyurethanes.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferred.embodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by reactingcertain hydroxyl containing phosphites and/or thiophosphates with anorganic polyisocyanate to form polyurethane. Preferably, phosphites areemployed so that the polyurethane produced has phosphite groupingstherein.

As the phosphorus containing polyhydroxyl compounds for reaction withthe organic polyisocyanate there can be employed (1) compounds havingthe Formula I and (2) the phosphite, phosphate and thiophosphate estersof an alkaneether polyol having 3 to 6 hydroxyl groups and being theether of an alkane polyol having 3 to 6 carbon atoms and 3 to 6 hydroxylgroups with an alkylene glycol or polyakylene glycol, said phosphite,phosphate or thiophosphate having at least 6 free hydroxyl groups.

In Formula I, R R R and R and R are residues of polypropylene glycol,polyethylene glycol, polytetrameth- 3,220,961 Patented Nov. 30, 1965ylene glycol or other polyalkylene gycol from which one of the hydroxylhydrogens has been removed. R and R are the residues of polyethyleneglycol, polypropylene glycol, polytetramethylene glycol or otherpolyalkylene gycol from which the two hydroxyl groups have been removed,it is zero or an integer and X is nothing, oxygen or sulfur. Preferably,X is nothing, i.e.,- the compounds are phosphites. Preferably, all of RR R R R R and R are the residues of polypropylene glycol. The compoundsvwithin Formula I are normally prepared as mixtures. Generally, over 50%,and usually the vast majority of the free hydroxyl groups present, e.g.,about are secondary hydroxyl groups when polypropylene glycol is theesterifying alcohol. R R R R and R in such case normally have thestructure HOCHOH2O(CH CHO)xH Where X is an integer. It has been foundthat superior polyurethanes are obtained when employing phosphitescontaining such secondary hydroxyl groups as reactants. In the specificexamples the polypropylene glycol derivatives used had about 90%secondary alcohol groups.

The compounds within Formula I which can be employed can be made in themanner set forth in application Serial No. 129,529. When it is desiredto have end groups other than those from polypropylene glycol, then thepolypropylene glycol used as the starting material for making thephosphite esters should be replaced in an equimolar amount by theappropriate other glycol, e.g., diethylene glycol or polyethylene glycol3000.

Also, there can he used glycol copolymers, e.g., block polymers withunits or ethylene glycol and propylene glycol. Typical examples of suchblock polymers are disclosed and claimed in Lundsted Patent 2,674,619.Examples of such block polymers are the block copolymer of Example 1 ofLundsted (polyoxypropylene glycol 1620 molecular weight+17.4% ethyleneoxide based on the total product weight), and the block copolymers ofLundsted Example 2, runs 1, 3 and 8.

Examples of polymeric phosphites, phosphates and thiophosphates withinFormula I and which can be employed to react with an organicpolyisocyanate include phosphites and phosphates such as dipropyleneglycol tetrol diphosphite, dipropylene glycol tetrol diphosphate,dipropylene glycol pentol triphosphate, dipropylene glycol pentoltriphosphite, dipropylene glycol hexol tetraphosphite, dipropyleneglycol hexol tetraphosphate, dipropylene glycol heneicosoldecaphosphite, tripropylene glycol tetrol diphosphite, tripropyleneglycol hexol tetraphosphite, polypropylene glycol 425 tetrol diphosphite(polypropylene glycol 425 is a mixture of polypropylene glycols havingan average molecular weight of about 425), polypropylene glycol 425tetrol diphosphate, polypropylene glycol 425 hexol tetraphosphite,polypropylene glycol 425 pentol triphosphite, polypropylene glycol 425pentol triphosphite, polypropylene glycol 425 octol hexaphosphite,polypropylene glycol 2025 hexol tetraphosphate, polypropylene glycol1025 tetrol diphosphite (polyproylene glycol 1025 is a mixture ofpoly-propylene glycols having an average molecular weight of about1025), polypropylene glycol 1025 pentol triphosphite, polypropyleneglycol 1025 hexol tetraphosphite, polypropylene glycol 1025 heptolpentaphosphite, polypropylene glycol 2025 tetrol diphosphite(polypropylene glycol 2025 is a mixture of polypropylene glycols havingan average molecular weight of about 2025), polypropylene glycol .2025pentol triphosphite, polypropylene glycol 2025 hexol tetraphosphite,polypropylene glycol 3000 tetrol diphosphite, polypropylene glycol 3000pentol triphosphite, polypropylene glycol 5000 tetrol diphosphite,dipropylene glycol tetrol diethylene glycol diphosphite (Where the 4hydroxy containing end groups are dipropylene glycol residues and theconnecting links between the two phosphorus atoms are the diethyleneglycol grouping), diethylene glycol tetrol diphosphite, diethyleneglycol pentol triphosphite, triethylene glycol tetrol diphosphite,polyethylene glycol 1000 tetrol diphosphite, ditetramethylene glycoltetrol diphosphite and thiophosphates such as dipropylene glycol tetroldithiophosphate, dipropylene glycol tetrol phosphite thiophosphate,dipropylene glycol tetrol phosphate thiophosphate, dipropylene glycolpentol trithiophosphate, dipropylene glycol hexol tetrathiophosphate,dipropylene glycol octol hexathiophosphate, tripr-opylene glycol tetroldithiophosphate, tripropylene glycol hexol tetrathiophosphate,polypropylene glycol 425 tetrol dithiophosphate, polypropylene glycol425 hexol tetrathiophosphate, polypropylene glycol 1025 tetroldithiophosphate, polypropylene glycol 1025 hexol tetrathi-ophosphate,polypropylene glycol 2025 tetrol dithiophosphate, polypropylene glycol2025 hexol tetrathiophosphate, triethylene glycol tetrol dithiophosphateand polyethylene glycol 1000 pentol trithiophosphate.

Examples of suitable phosphites, phosphates and thiophosphates ofalkaneetherpolyols in group (2) which can be employed with an organicpolyisocyanate are made in the manner set forth in application 129,529and include tris (propylene oxide-1,2,6 hexanetriol adduct) phosphitewherein the adduct has a molecular weight of 750 (tris LHT-240phosphite), the tris esters of phosphorus acid and the adducts ofpropylene oxide and 1,2,6- hexanetriol having molecular weights of 1500,2400 and 4000 (tris LHT-ll2 phosphite, tris LHT-67 phosphite and trisLET-42 phosphite respectively), tris (propylene oxide-glycerine adduct)phosphite where the adduct has a molecular weight of 1000 (tris LG-168phosphite), the corresponding phosphite of the propylene oxideglycerineadduct having a molecular weight of 3000 (tris LG-56 phosphite), tris(sorbitol-propylene oxide adduct) molecular weight 1000 phosphite, tris(trimethylolpropanepropylene oxide adduct molecular weight 1700)phosphite, tris (ethylene oxide-glycerine adduct molecular weight 1000)phosphite, tris (trimethylolethane-propylene oxide adduct molecularweight 2000) phosphite, tris (mannitolpropylene oxide adduct molecularWeight 3000) phosphite, tris (sorbitol-propylene oxide adduct molecularweight '3000) phosphite, tris (sorbitol-propylene oxide adduct molecularweight 2500) phosphite, tris (pentaerythritolpropylene oxide adductmolecular weight 1000) phosphite; tris (pentaerythritol-propylene oxideadduct molecular weight 750) phosphite, tris (pentaerythritol-propyleneoxide adduct molecular weight 2000) phosphite as well as thecorresponding pentaerythritol-propylene oxide adducts of molecularweights 400, 450, 500, and 600 (Pluracols PeP). These adduct phosphitescan also be named as phosphites of the ether of propylene glycol,ethylene glycol, polyethylene glycol or polypropylene glycol, and thepolyhydric alcohol employed, e.g., tris (glycerine-polypropylene glycol3000 ether) phosphite (tris LG-56 phosphite), adducts oftrimethylolpropane and propylene oxide of molecular Weights 300, 400,700, 1500, 2500 and 4000 (Pluracol TP); Also there can be used adductsof ethylene oxide and propylene oxide, such as those in theaforementioned Lundsted patent, e.g., Example 1 and Example 2 runs 1, 3and 8 thereof. Thus, there can be used the adduct of polyoxypropylenepolymer molecular weight 926 with 45% by weight of polyoxyethylenecontent. The invention further includes as phosphites which can beincludede in group (2) as suitable reactants with the organicpolyisocyanate, polyphosphites such as those set forth in Examples 41and 42 of the parent application, e.g., LHT-240non-oldiphosphite,LET-240 dodeca-ol triphosphite, the diphosphite of isorbitol-propyleneoxide ad-duct having .a molecular weight to 1000; the triphosphite ofsorbitol-propylene oxide adduct having a molecular weight of 1000,

the diphosphite of pentaerythritol-propylcne oxide adduct having amolecular weight of 1000) or the adducts of molecular weights 400, 450,500 and 600) and the triphosphite of pentaerythritol-propylene oxideadduct having a molecular weight of 1000 (or the adducts of molecularweights 400, 500 and 600) as well as the diphosphite oftrimethylolpropane-propylene oxide adduct molecular weights 300, 400,700, 1500, 2500 and 4000, and the corresponding triphosphites.

As examples of suitable thiophosphates and phosphates in group (2) therecan be mentioned tris LHT-42 thiophosphate, tris LHT-42 phosphate, trisLHT-67 phosphate, tris LHT-240 phosphate, tris LHT67 thiophosphate, trisLHT-112 thiophosphate, tris LHT240 thiophosphate, tris LG-56thiophosphate, tris LG-168 thiophosphate, tris LG-56 phosphate, trisLG-l68 phosphate, tris-pentaerythritol-propylene oxide 450 phosphate andthe corresponding thiophosphate, tris-trimethylolpropanepropylene oxidemolecular weight 700 phosphate and the corresponding thiophosphate.

The preferred compounds for forming polyurethanes whether within FormulaI or group (2) are phosphites and the most preferred are the phosphitesof derivatives of polypropylene glycol which phosphites have a majorityof secondary alcohol groups.

In the following description of reaction procedure, it is to beunderstood that when reference is made to the use of phosphites, sincethese are the preferred reactants, that the same reaction conditions canbe used with the phosphates and thiophosphates.

The phosphites, e.g., polyphosphites set forth supra (or thethiophosphates) can be the sole hydroxyl reactant present or they can beused in admixture with other polyhydroxy compounds (polyols) in formingthe polyurethanes. Foamed polyurethanes can be obtained by addingwaterprior to or simultaneously with the addition of the polyisocyanate.

Alternatively, foams can be prepared by uniformly distributing aliquefied halogen substituted alkane containing at least one fluorineatom in its molecule and having a boiling point at one atmospherepressure not higher than F. and preferably not lower than 60 F. ineither the phosphite (or mixture of phosphite and other polyhydroxycompound) reactant or the polyisocyanate reactant and then mixing thereactants and permitting the temperature of the mixture to rise duringthe ensuing reaction above the boiling point of the liquefied gas toproduce a porous polyurethane. Such fluorine containing compoundsinclude dichlorodifluoromethane, dichloromonofluoromethane,chlorodifluoromethane, and dichlorotetrafluoroethane. The foams can beformed with such fluorine containing compounds in the manner describedin General Tire British Patent 821,342.

Foamed polyurethanes can be made by either the one shot or two stepprocedures. In the case of the reaction of phosphites having a hydroxylnumber above in order to form a good flexible foam it is often desirableto employ the two step procedure unless an additional polyhydroxyreactant is added to lower the hydroxyl number of the hydroxy reactantsto below 125 and preferably below 100, e.g., as low as 25, butpreferably at least 35.

In preparing urethane foams according to the invention a rigid foam ismade utilizing a polyol phosphite of the type set forth supra (ormixture of such phosphite and another polyhydroxy containing compound)having a hydroxyl number of 350-760; a semi-rigid foam is prepared ifthe hydroxyl number is 75-350, and a flexible foam is prepared if thehydroxyl number is 35-75.

The polyurethanes prepared according to the present invention aresolids. They have good flame-proofing properties and in the foamed formare useful as linings for textiles, e.g., coats, suits and dresses,insulation in building construction, upholstery filling material,pillows, hair curlers, brushes, carpet underlays or backings, shockabsorbent filling for packages, etc.

The unfoamed polyurethane products are useful whereever elastomericpolyurethanes can be employed with the advantage of improved flame andfire resistance. The elastomers in thread form can be employed in makinggirdles. The unfoamed polyurethanes are suitable for molding cups andother articles, and as protective coatings for steel, wood and glass.

The polyurethanes can be cured in conventional fashion, e.g., in an ovenat 110 C.

As examples of organic polyisocyanates which can be employed to make thepolyurethane there can be employed toluene2,4-diisocyanate,toluene-2,6-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, diphenylmethane-4,4-diisocyanate, 4-chlorol ,3-phenylene-diisocyanate,v4-isopropyl-l,3-phenylene-cliisocyanate,4-ethoxy-1,3-phenylene-diisocyanate, 2,4-diisocyanate-diphenylether,3,3'-dimethyl 4,4'-diisocyanatodiphenyl methane, mesitylenediisocyanate, durylene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), benzidine diisocyanate, o-nitrobenzidinediisocyanate, 4,4'-diisocyanatodibenzyl,3,3'-bitolylene-4,4-diisocyanate, 1,5-naphthalene diisocyanate,tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylenediisocyanate, toluene-2,4,6-triisocyanate, tritolylmethenetriisocyanate, and 2,4,4-triisocyanatodiphenyl ether, the reactionproduct of toluene diisocyanate with trimethylolpropane at an NCO/ OHratio of 2:1 (Mondur CB), the reaction product of toluene diisocyanatewith 1,2,6-hexanetriol at an NCO/ OH ratio of 2: 1, the reaction productof toluene diisocyanate with the polyol phosphite at an NCO/ OH ratio of2: 1, e.g., when the polyol phosphite is dipropylene glycol tetroldiphosphite or tris (pentaerythritol-polypropylene glycol ether)phosphite.

Alternatively, as the polyisocyanate there can be used prepolymers madeby reacting one or more of the above polyisocyanates with a polyhydroxycompound such as a polyester having terminal hydroxyl groups, apolyhydric alcohol, glycerides, hydroxy containing glycerides, etc. Theprepolymers should have terminal isocyanate groups. To insure this it isfrequently desirable to employ an excess of 5% or more of thepolyisocyanate in forming the prepolymer.

Typical examples of such prepolymers having isocyanate end groups arethose formed from toluene diisocyanate and polyhydroxy compounds. Unlessotherwise indicated, in the illustrative examples a mixture of 80% 2,4-isomer and 20% 2,6-isomer of toluene diisocyanate was employed in makingthe prepolymer. Thus, there can be used the prepolymers from toluenediisocyanate and castor oil, toluene diisocyanate and blown tung oil (orblown linseed oil or blown soya oil), toluene diisocyanate and thepolyester of ethylene glycol, propylene glycol and adipic acid having amolecular weight of 1900 described in Example I of Kohrn Patent2,953,839, as well as the isocyanate terminated prepolymers in ExamplesII-VHI, inclusive, of the Kohrn patent, toluene diisocyanate andpolytetramethylene glycol (1000 molecular weight), toluene diisocyanateand polypropylene glycol (molecular weight 2025), toluene diisocyanateand dipropylene glycol, toluene diisocyanate and polypropylene glycol(molecular weight 1025), toluene diisocyanate and LG-56(glycerine-propylene oxide adduct having a molecular weight of 3000),toluene diisocyanate and 1,2,6-hexanetriol-propylene oxide adductshaving molecular weights of 500, 700, 1500, 2500, 3000 and 4000,hexamethylene diisocyanate and pentaerythritol, toluene diisocyanate andpolyethylene sebacate, toluene diisocyanate and a mixture of 98%polypropylene glycol (molecular weight 190) with 2% 1,2,6-hexanetriol,toluene diisocyanate and a copolymer of ethylene oxide and propyleneoxide having a molecular weight of 2020, toluene diisocyanate andglyceryl adipate phthalate polymer, toluene diisocyanate and a mixtureof polypropylene ether glycol molecular weight 995 and castor oil asdescribed in Example 2 of Kane Patent 2,955,091, as well as the otherprepolymers set forth in Examples 1 and 3-11 of Kane, toluenediisocyanate and 0 polypropylene ether glycol (molecular weight 1800) ofExample I of Swart Patent 2,915,496 and the prepolymers of Examples II,III, VI and VIII of the Swart patent. Toluene diisocyanate and tris(dipropylene glycol) phosphite; toluene diisocyanate and tris(polypropylene glycol 2025) phosphite.

As previously stated, the polyol phosphites of the present invention canbe the sole hydroxyl reactant present or they can be used in admixturewith other polyhydroxyl compounds in forming the polyurethanes. Examplesof such compounds are polyethylene glycols having molecular weights of400 to 3000, polypropylene glycols having molecular weights of 400 to3000, ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol,thiodiglycol, glycerol, trimethylolethane, trimethylolpropane, ethertriols from glycerine and propylene oxide having molecular weights of1000 and 3000 (available commercially as LG-l68 and LG56, respectively),ether containing triols from 1,2,6-hexanetriol and propylene oxidehaving molecular weights of 750, 1500, 2400, and 4000 (availablecommercially as LET-240, LHT-112, LHT-67 and LHT- 42, respectively),sorbitol-propylene oxide adduct having a molecular weight of 1000,pentaerythritol-propylene oxide adduct having a molecular weight of1000, trimethylol phenol, oxypropylated sucrose, triethanolamine,pentaerythritol, diethanolamine, castor oil, blown linseed oil, blownsoya oil, N,N,N,N-tetrakis (Z-hydroxyethyl) ethylenediamine,N,N,N,N'-tetrakis (Z-hydroxypropyl) ethylenediamine, mixed ethyleneglycol-propylene glycol adipate resin (molecular weight 1900),polyethylene adipate phthalate, polyneopentylene sebacate, the productmade by reacting an excess of 1,4-butanediol with adipic acid andincluding a small amount of a triol, e.g., one molar equivalent oftrimethylol propane for each 3000 to 12,000 molecular weight units ofpolyester, polyester from 16 moles adipic acid 16 moles diethyleneglycol and 1 mole of trimethylol propane, oxypropylated p-tertiarybutylphenolformaldehyde resin of Example 2b of De Groote Patent2,499,365 and the other oxyalkylated resins of De Groote, tris(dipropylene glycol) phosphite, and tris (polypropylene glycol 2025)phosphite.

From 5 to by weight of the hydroxyl component can be the polyolphosphites of the present invention, i.e., Formula I and group (2)supra. As previously indicated when employing a polyol phosphite havinga hydroxyl number above in order to form good fiexible foams preferably5-85% of the hydroxyl containing substance is such material and thebalance is tris poly propylene glycol 2025 phosphate, or LG-56 or otherpolyol which will reduce the hydroxyl number to below 100 and preferablyto between 30 and 75, if the polyol phosphite has too low a hydroxylnumber then it can be blended with another polyol phosphite or polyol tobring the hydroxyl number in the proper range for forming a good foam.

The polyol phosphites also can be employed as light stabilizers forpolyurethane resins made from any of the nonphosphorus containingpolyols set forth above. For such use the polyol phosphite is employedin an amount of from 01-15% by weight of the polyol, e.g., 2.2% byweight of dipropylene glycol tetrol diphosphite is added to 14.4 gramsof LG-56. Conventional catalysts and surfactants are also employed. Thismixture is stable and can be added to 5.2 grams of toluene diisocyanateand 0.37 gram of water to form a light stable foamed polyurethane. Thedipropylene glycol tetrol diphosphite and the other polyol phosphitesnot only act to stabilize the nonphosphorus containing polyol employedas well as the polyurethane product but also serve as reactants.

In preparing the cured and/or foamed polyurethanes any of theconventional basic catalysts, i.e., N-methyl morpholine, N-ethylmorpholine, 1,2,4-trimethylpiperazine, trimethyl amine, triethyl amine,tributyl amine and other trialkyl amines, the esterification product of1 mole of adipic acid and 2 moles of diethylethanolamine, triethyl aminecitrate, 3-morpholinepropionamide, 1,4-bis (2-hydroxypropyl) 2methylpiperazine, Z-diethylaminoacetamide, 3-diethylaminopropionamide,diethylethanolamine, triethylenediamine, N,N,N',N-tetrakis(Z-hydroxypropyl) ethylenediamine (Quadrol), N,N'dimethylpiperazine, N,N-dimethylhexahydroaniline, tribenzylamine and sodium phenolate. Therecan also be used tin compounds, e.g., hydrocarbon tin acylates such adibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate,tributyltin monolaurate, dimethyltin diacetate, dioctyltin diacetate,dilauryltin diacetate, dibutyltin maleate, hydrocarbon tin alkoxides,e.g., dibutyltin diethoxide, dibutyltin dimethoxide, diethyltindibutoxide as well as other tin compounds, e.g., octylstannoic acid,trimethyltin hydroxide, trimethyltin chloride, triphenyltin hydride,triallyltin chloride, tributyl ti fluoride, dibutyltin dibromide,bis(carboethoxymethyl) tin diiodide, tributyltin chloride, trioctyltinacetate, butyltin trichloride, octyltin tris-(thiobutoxide), dimethyltinoxide, dibutyltin oxide, dioctyltin oxide, diphenyltin oxide, stannousoctanoate, stannous oleate, as well as the other tin compounds set forthin Hostettler French Patent 1,212,252.

Conventional surfactants can be added in the amount of 1% or less, e.g.0.2% by weight of the composition. The preferred surfactants aresilicones, e.g. polydimethyl siloxane having a viscosity of 3 to 100centistokes, triethoxydimethyl polysiloxane, molecular weight 850copolymerized with a dimethoxypolyethylene glycol having a molecularweight of 750, as well as any of the other siloxanes disclosed inHostettler French Patent 1,212,252.

Unless otherwise indicated, all parts and percentages are by weight.

In preparing polyurethanes the following values are of interest.

Molecular OH OH equiv- Compound weight number alent in grams*Dipropylene glycol tetrol diphosphite 726 309 2. G1 Dipropylene glycolpentol triphosphito 1, 022 274 2. 95 Polypropylene glycol 425 tetroldiphosphite 2, 181 103 7. 56 Dipropylene glycol hexol tetraphosphite 1,318 256 3. 17 Polypropylene glycol 425 pentol triphosphite 3, 059 92 8.77 Tripropylene glycol tetrol diphosphite 1, 018 220 3. 68 Polypropyleneglycol 1025 tetrol diphosphite 5, 181 43 18. 8 Polypropylene glycol 2025tetrol diphosphite 10, 181 22. 2 36. 4 Polypropylene glycol 1025 pentoltriphosphite 7, 259 38. 6 20. 9 LET-240 hexolphosphite- 2, 100 160 5.03LG-168 hexol phosphite 3, 028 111 7. 28 Bis dipropylene glycolpentaerythritol diphosphite 460 243 3. 31 Dipropylene glycol tetroldithio- Bphosphatei 1 i 1g 790 284 2. 82

is p ypropy one g yeo pentaerythritol diphosphite. 1, 350 83 9. 7LHT-240 nonol diphosphite 3, 806 133 6. 06 LHT-240 dodeca-oltriphosphite 5, 334 126 6. 4 Tris(sorbitol-propy1ene oxideadduct)phosphite 3, 028 278 2. 9 Tris (pentaerythritol-polypropyleneglycol ether)phosphite 1, 230 410 1. 96

Equivalent to 14.4 grams of LG-56 (glyeerinepropylene oxide adduct;triol with hydroxyl number of 56).

In the following examples, unless otherwise indicated, the toluenediisocyanate employed was a mixture of 80% of the 2,4-isomer and 20% ofthe 2,6-is0mer.

In preparing one shot foams there was utilized the following standardformulation:

Polyol as indicated.

This mixture is designated in the following examples as Formulation A.

Foams were made by adding Formulation A to 5.2 grams of the toluenediisocyanate. The foams were then cured in a C. oven for about 20minutes.

In the comparison or control example there was employed 14.4 grams ofLG--56 as the polyol. Utilizing a 10 ounce cup the LG-56 foam rose 1.5inches above the top of the cup.

Example 1 The polyol used in Formulation A was a mixture of 1.3 ml.(about 1.3 grams) of dipropylene glycol tetrol diphosphite and 7 gramsof LG-56. Upon addition of 5.2 grams of toluene diisocyanate there was arapid cream time and rise. A nice foam was produced having closed cells.

In Example 1 and the other foam examples silicone fluid 520 was equallyetfective when employed in place of the polydimcthyl siloxane in thesame amount.

Example 2 The polyol used in Formulation A was a mixture of 1.4 ml.(about 1.4 grams) of dipropylene glycol pentol triphosphite and 7 gramsof LG-56. Upon addition of 5 .2 grams of toluene diisocyanate there wasa rapid cream time and rise. The product had closed cells which werebroken by hand crushing. After curing the product had nice tensilestrength and hand properties.

Example 3 The polyol used in Formulation A was a mixture of 1.3 ml. ofdipropylene glycol tetrol diphosphite and 7 grams of polypropyleneglycol 2025. After adding 5.2 grams of toluene diisocyanate the foamedproduct had closed cells.

Example 4 The polyol used in Formulation A was 4.9 grams of LET-240hexol phosphite. After adding 5.2 grams of toluene diisocyanate therewas a moderate foam rise which yielded a rigid foam. It was fairlystrong after curing for 1 hour at C. The white product appeared to be agood foam with low density.

Example 5 The polyol used in Formulation A was a mixture of 2.5 grams ofLHT-240 hexol phosphite and 7.2 grams of polypropylene glycol 2025.After adding 5.2 grams of toluene diisocyante a foamed open cell productof the semi-rigid type was produced.

Example 6 The procedure of Example 5 was repeated but the polypropyleneglycol 2025 was replaced by 7.2 grams of LG56. A closed cell semi-rigidfoam was produced.

Example 7 42 ml. of octane solvent were heated to 70% C. and then 10.0ml. of his polypropylene glycol 425-pentaerythritol diphosphite(molecular weight 1200-1500) added. The mixture was heated to boilingand a little water present azeotroped out; Then 1.74 ml. of toluenediisocyanate was added and the mixture refluxed for 2 hours. Next 0.65ml. of water was added and the mixture refluxed an additional 30minutes. This precipitated a mass of polymer granules. The mixture wascooled to 50 C. and the product filtered off and air dried in an oven at50 C. The product was ground in a mortar with a pestle to give a rubberysubstance. This was placed in a Carver press at 15,000 psi to give ahard rubber-like block. It was translucent white in color and appearedto be a good elastomer. The product was suitable to mold cups and couldbe employed to spin threads.

In place of his polypropylene glycol 425-pentaerythritol diphosphitethere can be used other bis polypropylene glycol pentaerythritoldiphosphites, e.g., bis dipropylene glycol pentaerythritol diphosphite(molecular weight 460) bis polypropylene glycol 1025-pentaerythritoldiphosphite and bis polypropylene glycol 2025-pentaerythritoldiphosphite. Less preferably the corresponding polyethylene glycolpentaerythritol diphosphites can be employed.

The bis polypropylene glycol pentaerythritol disphosphites and the likecan be employed to form polyurethane foams either alone or admixed withother polyols, e.g., 4.8 grams of his polypropylene glycol425-pentaerythritol diphosphite and 7.2 grams of LG56 can be used as thepolyol in Formulation A to react with 5.2 grams of toluene diisocyanate.

Example 8 The polyol used in Formulation A was 6 grams of LHT-240 nonoldiphosphite. After adding 5.2 grams of toluene diisocyanate a rigidfoamed product was obtained.

Example 9 The polyol used in Formulation A was a mixture of 1.4 grams oftris (sorbitol-propylene oxide adduct, molecular weight 1000) phosphite(also called tris sorbitolpolypropylene glycol ether-phosphite) and 7.2grams of polypropylene glycol 2025. After adding 5.2 grams of toluenediisocyanate a foamed product was obtained.

Example 10 The polyol used in Formulation A was a mixture of 2.4 gramsof tris (pentaerythritol-propylene oxide adduct, molecular weight 1000)phosphite and 7.2 grams of LG-56. After adding 5.2 grams of toluenediisocyanate a foamed product was obtained.

Example 11 The polyol used in Formulation A was 18.8 grams ofpolypropylene glycol 1025-tetrol diphosphite. After adding 5.2 grams oftoluene diisocyanate a foamed product was produced.

Example 12 Formulation A was used omitting the water and employing 5.15grams of LI-lT-240 hexol phosphite. There was then added 5.2 grams oftoluene diisocyanate and the mixture allowed to react to form aprepolymer. There was then added 0.37 ml. of water and a nice light foamwas obtained which was cured at 110 C.

Example 13 72.6 grams (0.1 mole) of dipro-pylene glycol tetroldiphosphite, 48.3 grams (0.22 mole) of toluene diisocyanate (80/202,4/2,6-isomer ratio) were heated together at 90 C. for one hour anddissolved in 100 ml. of dimethyl formamide and portions of the productwere painted on (a) a glass petri dish, (b) a steel plate, and (c) apiece of wood. The samples were placed in an oven at 120 C. for one hourto remove the solvent and then air cured for 4 hours. In all cases aresin coating Was obtained which did not burn and acted as a fireretardant paint.

Example 14 The polyol employed in Formulation A was a mixture of 4.3grams of polypropylene glycol 425-pentol triphosphite and 7 grams of apolyester of molecular weight about 2000, hydroxyl number of 62.4 andacid number of 0.4 (made from adipic acid and a mixture of 50%diethylene glycol and 50% 1,5-pentanediol) to produce a nice cured foam.

Example 15 The polyol employed in Formulation A was 14 grams of LG-56 towhich had been added 0.2 gram of polypropylene glycol 425-tetroldiphosphite as a stabilizer. After addition of the 5.2 grams of toluenediisocyanate there was produced a nice foam which was cured at 110 C.for minutes.

10 Example 16 The procedure of Example 15 was repeated but thepolypropylene glycol 425-tetrol diphosphite was replaced by 0.1 gram ofbis dipropylene glycol pentaerythritol diphosphite.

Example 17 Monomeric and polymeric esters can be made by reactingtetramethyl cyclobutanediol 1,3 With (1) a 3,9-dihydroca-rbonoxy2,4,8,l0 totraoxa 3,9-diphosph-aspiro-(5,5)- undecane or (2) a mixtureof a trihydrocarbon or trihaloaryl phosphite and pentaerythritol. Thereaction can be catalyzed by the addition of 0.1 to 5% of an alkalimetal alcoholate or phenolate or 0.1 to 5% of a dihydrocarbon phosphiteor dihaloaryl phosphite based on the weight of the phosphorus compound.Any of the catalysts of these groups set forth in application Serial No.111,899, filed May 23, 1961, now Patent No. 3,053,878, can be used. Themolecular weight of the polymer will depend on the mole ratio of thereactants. When the tetramethyl cyclobutanediol and spiro compound areemployed in a mole ratio of 1:1 the highest molecular weight polymersare formed. As the mole ratio departs from unity the molecular weightsdecrease and at a mole ratio of 2:1 or higher, for example a monomericproduct is produced.

Thus a high molecular weight polymer is produced by heating 2.00 molesof tetramethyl cyclobutanediol 1,3 with 2.07 moles of diphenylpentaerythritol diphosphite in the presence of 5 grams (0.02 mole) ofdiphenyl phosphite. The mixture is heated at 220 C. at 10 mm. until theyield of phenol obtained by distillation is almost quantitative. Thesolid polymer produced is more resistant to hydrolysis than the polymersusually produced by reacting a dihydric alcohol with diphenylpentaerythritol diphosphite. It can be molded to form a cup.

A similar product is produced by replacing the diphenyl pentaerythritoldiphosphite by 2.07 moles of didecyl pentaerythritol diphosphite andremoving the decyl alcohol formed by distillation at 10 mm.

A monomer can be formed by heating 2 moles oftetramethylcyclobutanediol-1,3 with 1 mole of diphenyl pentaerythritoldiphosphite in the presence of 0.02 mole of diphenyl phosphite andheating at 10 mm. until 1 mole of phenol is romeved by distillation.This reaction can also be carried out by adding 2.5 moles of thetetramethylcyclobutanediol-1,3 and subsequently removing the excess 0.5mole of the cyclobutanediol by distillation.

The monomer and polymers of Example 17 are useful as stabilizers forpolyethylene, polypropylene, polyurethanes and the like.

Example 18 Tris (2,2,4,4-tetramethylcyclobutanediol-1,3) phosphite ismade by reacting 1 mole of triphenyl phosphite, 3 grams of diphenylphosphite (0.01 mole, catalyst) and 3.3 moles (a 10% excess) of2,2,4,4-tetramethylcyclobutanediol-1,3 in vacuo at 10 mm. The 3 moles ofphenol formed were removed by distillation at this pressure as was the10% excess tetramethyl cyclobutanediol to leave the tris(tetramethylcyclobutanediol-1,3) phosphite as a viscous liquid residue.This compound can be reacted with toluene diisocyanate and the otherpolyisocyanates mentioned supra to form flame proof polyurethane resins.Thus in Formulation A above there can be used a mixture of 1 gram oftris (tetramethylcyclobutanediol) phosphite and 7 grams of LG-56. Uponaddition of 5 .2 grams there was obtained a good solid foam.

The tris (tetramethylcyclobutanediol) phosphite also can be used to formpolyurethane prepolymers, e.g., by omitting the water from Formulation Aand employing 2.0 grams of the tris (tetramethylcyclobutanediol)phosphite as the polyol and then adding 5.2 grams of toluenediisocyanate. After the mixture is allowed to react to form a prepolymerthen 0.37 ml. of water is added to produce a foam.

The polyurethane thus produced was a flame resistant rigid foam whichcould be used as insulation in building construction, etc.

The tris (tetrarnethylcyclobutanediol) phosphite also can be employed toform polyesters or can be used with epoxy compounds in forming resins.

Tris (tetramethylcyclobutanediol) phosphite has the H3 CH3 3 Thefollowing examples are directed to phosphonates and to flame resistantpolyurethanes made therefrom. The phosphonates also can be used to formflame resistant polyesters by reacting with polybasic acids, e.g.,terephthalic acid, phthalic acid and adipic acid. Such polyester can beemployed for example as protective coatings for wood, metal or the like.The polyurethanes can be foamed in the manner previously set forth toform flame resistant foams useful as building insulation, clothinginsulation or any other of the other uses previously set forth. Theunfoamed polyurethanes can be employed as protective coatings for woodOr metal.

The phosphonates can also be used in epoxy resin formulation.

Example 19 Dipropylene glycol hydroxypropoxypropane phosphonate wasprepared by treating tris dipropylene glycol phosphite with 5 molpercent of n-butyl bromide at 125135 C. for 8 hours at which time therewas no increase in P=O bond in the infrared analysis. Volatile materialwas stripped oil at 150 C. and 10 mm. The liquid residue was essentiallypure bis dipropylene glycol hydroxypropoxypropane phosphonatecontaminated with about 5% of dipropylene glycol butane phosphonate. Thedipropylene glycol phosphonate had the formula CH3 CH3 CH3 CH3 HO(EHCHzO-CHgHO-l HCHzO CHzHOH HO CHCHzO-CH CHO Hz Ha Example 20 1 mole ofbis dipropylene glycol hydrogen phosphite was reacted with 1 mole ofpropylene oxide in the presence of grams of potassium carbonate at 75 C.to produce bis dipropylene glycol 2-hydroxypropane phosphonate. Similarreactions can be carried out with ethylene oxide or butylene oxide andutilizing other alkaline catalysts, e.g., slaked lime, tetramethylguanidine and pentamethyl guanidine.

Example 21 1 mole of tris dipropylene glycol phosphite was heated withfive moles of propylene chlorhydrin 1-chloro-2- hydroxypropane) for 8hours at 125l35 C. The excess propylene chlorhydrin and thechloropropylhydroxy propyl ether formed were stripped off in a vacuummm.) and bis dipropylene glycol Z-hydroxypropanephosphonate recovered asthe residue.

Bis dipropylene glycol hydroxyethane phosphonate can be obtained bysubstituting ethylene chlorohydrin for propylene chlorohydrin in thisreaction. Propylene bromohydrin can be employed in place of propylenechlorohydrin. If the amount of propylene chlorohydrin is reduced, e.g.,to a l to 1 mole ratio with the tris (dipropylene glycol) phosphite thenthere is obtained a mixture of his dipropylene glycol Z-hydroxy propanephosphonate and bis dipropylene glycol hydroxypropoxypropane phosphonateas the product.

l 2 Example 22 The reaction set forth in Example 20 can also be carriedout with the polymeric dipropylene glycol hydrogen phosphites. Thus onemole of trimeric dipropylene glycol hydrogen phosphite can be reactedwith 3 mols of propylene oxide in the presence of 5 grams of tetramethylguanidine to produce the corresponding hydroxypropane phosphonateaccording to the equation H2 H2 CHOH CHOH CHOH CH3 CH3 CH3 Where DPG isdipropylene glycol with a hydroxyl hydrogen removed and DPG* isdipropyleneglycol with both be prepared by heating bis dipropyleneglycol hydrogen hydroxyl hydrogens removed. The starting phosphite canbe prepared by heating bis dipropylene glycol hydrogen phosphite in avacuum and distilling off the requisite amount of dipropylene glycolformed.

In place of propylene oxide there can be used ethylene oxide andbutylene oxide. If an excess of alkylene oxide is used in Examples 20and 22 then further etherification of any of the free hydroxyl groupswill occur. Normally this is not preferable since the amount ofphosphorus in the molecule is reduced.

Example 23 Example 19 was repeated replacing the tris dipropylene glycolphosphite by tris tripropylene glycol phosphite to produce tripropyleneglycol 2-hydroxypropoxypropoxy propane phosphonate.

In similar fashion tris LHT-240 phosphite can be rearranged to thecorresponding phosphonate.

Example 24 This product was reacted with 1 equivalent of bromine toobtain the corresponding 2,3 -dibromide.

Exam'ple 25 Dipropylene glycol tetrol diphosphite was treated with 2.5mole percent of butyl bromide until phosphonate formation appeared to becomplete (8 hours at 135 C.). Volatiles were stripped out at 10 mm.pressure. The light colored viscous liquid was a mixture of HOBO OROHPRP HORO OROH HORO OROH PROP HOBO OROH In a similar fashion tripropyleneglycol tetrol diphosphite is treated with butyl bromide to give ananalogous product.

The products of Examples 19-25 as previously stated can be reacted withorganic polyisocyanates to form polyurethanes. To reduce the hydrophylicproperties it has been found that it is preferable to have hydroxypropylor hydroxypropoxy propyl groups present rather than hydroxyethyl orhydroxyethoxyethyl groups.

To form polyurethanes in addition to the novel phosphonates of Examples19-25 there can also be used hydroxyalkyl and hydroxyalkoxyalkyl estersof hydrocarbon and halohydrocarbon phosponates such as the bis propyleneglycol ester of decanephosphonic acid, bis dipropylene glycol ester ofdecanephosphonic acid, bis dipropylene glycol ester of methanephosphonicacid, bis dipropylene glycol ester of cyclohexane phosphonic acid, bispropylene glycol ester of methanephosphonic acid, bis propylene glycolester of cyclohexanephosphonic acid, bis propylene glycol ester ofphenylphosphonic acid, bis dipropylene glycol ester of phenylphosphonicacid, bis dipropylene glycol ester of 4-chlorophenylphosphonic acid,tetra 2'-hydroxypropyl ethane-1,2-diphosphonate, tetra2-hydroxypropoxyethane-1,2-diphosphonate, tetra2-hydroxypropoxypropylethane-1,2-diphosphonate, tetra2-hydroxypropoxypropyl-1,4-butane diphosphonate, tetra 2'-hydroxypropoxypropyldecane-1,IO-diphosphonate, tetrapolypropylene glycolmolecular weight 2025 1,6-hexane diphosphonate, and tetrapolypropyleneglycol molecular weight 2025 1,6-hexane 2-diphosphonate.

Example 25a The polyol used in Formula A was a mixture of 1 gram of thediphosphonate prepared in Example 24 and 7 grams of LG-56. A foam wasmade upon addition of 5.2 grams of toluene diisocyanate.

Example 25b The procedure of Example 25:: was repeated replacing thediphosphonate with tetra 2-hydroxy-propoxypropyl-1,4-butanediphosphonate to obtain a foam.

Example 26 The polyol used in Formula A was a mixture of 1 gram of bisdipropylene glycol 2-hydroxypropoxypropane phosphonate and 7 grams ofLG-56. Upon addition of 5.2 grams of toluene diisocyanate a good foamwas produced.

Example 27 The polyol used in Formula A Was a mixture of 1 gram of hisdipropylene glycol 2-hydroxypropane phosphonate and 7 grams of LG-56.Upon addition of 5.2 grams of toluene diisocyanate a good foam wasproduced.

Example 28 Formulation A was used omitting the water and employing 1.89grams of bis dipropylene glycol 2-hydroxypropoxypropane phosphonate.There was then added 5.2 grams of toluene diisocyanate and the mixtureallowed to react to form a prepolymer. There was then added 0.37 ml. ofwater and a light foam produced which was cured at 110 C. for 20minutes.

It is also within the contemplation of the present invention to preparephosphite from poly alcoholic hydroxyl containing aromatic compounds.The phosphites thus prepared can be reacted with any of the above menl IO CHzCHOH O CH2CHO- l HCHr CHq P OCHzCHOH While the formula is writtenas if all of the bonds to the phosphorus are from the propylene glycolunit attached to the aromatic group on the number 3 carbon atom of thepropane chain, in actual practice a mixture or" isomeric compounds isobtained in which the bonds to the phosphorus can be fronrany of thethree propylene glycol units available on the starting aromaticcompound.

In place of employing pure 1,1,3-tris-[p-(2-hydroxypropoxy) phenyl]propane there can be employed the mixture of this compound and thepropylene oxide adduct of glycerine having a hydroxyl number of 625-650.This mixture is available commercially from Union Carbide Corporation asLK-380, hydroxyl number 372.3. The resulting phosphite is useful formaking rigid polyurethane foams.

Phosphites having 3 free hydroxyl groups can be prepared by reacting bishydroxypropoxyphenyl alkanes with triaryl or trialkyl phosphites. Anexample of such a product is the reaction product of triphenyl phosphitewith 2,2-[p-(Z-hydroxypropoxy) phenyl] propane, said reaction producthaving the formula C H 0 a nogm.o oom t o)1 This compound also can bereacted with polyisocyanates to form rigid polyurethanes.

In place of the hydroxy propoxy group there can be a hydroxy polypropoxygroup, e.g. by reacting the phenol with an excess of propylene oxideprior to formation of the phosphite. However, as previously stated forpreparing rigid polyurethanes it is preferred to employ phosphiteshaving a plurality of simple hydroxy propoxy groups.

Example 29 rose from 115 C. to 190 C. at 10 mm. There was recovered 1574grams of 95% pure phenol. The mixture was further heated at 190200 C.for one hour at mm. with nitrogen sparging. Twenty-six more grams ofdistillate were obtained. The residue weighed 2790 grams. It was treatedwith diatomaceous earth and activated clay to obtain a clear, dark amberproduct which was semi-solid at room temperature and a viscous liquid at100 C.

The product has a mixture of the phosphite of 1,1,3-tris-[p-(Lhydroxypropoxy) phenyl] propane having the formula indicatedsupra and the glycerine-propylene oxide adduct phosphite.

Either the pure phosphite of 1,1,3-tris-[p-(2-hydroxypropoxy) phenyl]propane or the pure glycerine-propylene oxide adduct phosphite can bemade by utilizing the appropriate pure material.

Example 30 There was employed 3 moles of 2,2-[p-(2-hydroxypropoxy)phenyl] propane and one mole of triphenyl phosphite with 3 grams ofdiphenyl phosphite. The phenol formed was removed in the mannerdescribed in Example 29, until about 280 grams of phenol had beenobtained. The residue in the pot was the phosphite of2,2-[p-(Z-hydroxypropoxy) phenyl] propane having the formula set forthabove.

Example 31 Three moles of the tetra 2-hydroxypropoxy ether ofpentaerythritol (pentaerythritol-propylene oxide adduct in a 1:4 moleratio), one mole of triphenyl phosphite and 5 grams of diphenylphosphite were heated to 150 C. in vacuo until about 3 moles of phenolwere stripped off. The product obtained was the tris(pentaerythritol-propylene oxide adduct) phosphite.

Example 32 Formulation A was used emitting the water and employing 3.14grams of the polyol phosphite prepared in Example 29 from LK-380 andtriphenyl phosphite having a molecular weight of 1350 and an OH numberof 250. The mixture was heated slightly to render it fluid. There wasthen added 5.2 grams of toluene diisocyanate with thorough mixing andthe mixture allowed to react to form a prepolymer. There was then added0.37 ml. of water and a nice light foam was obtained.

Example 33 Formulation A was used omitting the water and employing 4.8grams of the phosphite prepared in Example 30. There was then added 5.2grams of toluene diisocyanate with thorough mixing and the mixtureallowed to form a prepolymer. There was then added 0.37 ml. of water anda foam was obtained.

Example 34 Formulation A was used omitting the water and employing 5.0grams of the phosphite prepared in Example 31. There was then added 5.2grams of toluene diisocyanate and the mixture allowed to form aprepolymer. There was then added 0.37 ml. of water and a foam wasobtained.

In Example 25 the dipropylene glycol tetrol diphosphite can be replacedby dipropylene glycol pentol triphosphite to produce dipropylene glycolpentol triphosphonate, molecular weight 1026, OH number 274. Similarly,in Example 25 by employing polypropylene glycol 425 tetrol diphosphitethere is obtained polypropylene glycol 425 tetrol diphosphonate,molecular weight 2187, hydroxyl number 102.

Similarly, in Example 19 the tris dipropylene glycol phosphite can bereplaced by tris polypropylene glycol 425 phosphite to produce trispolypropylene glycol 425 phosphonate, molecular weight 1306, hydroxylnumber 129. Similarly, in Example 19 by employing tris LG 168 phosphitethere is obtained a hexol phosphonate having a molecular weight of 3000and a hydroxyl number of 112. correspondingly, hexol phosphonate ofmolecular weight 2100, hydroxyl number 160, is obtained by utilizingtris LHT-240 phosphite in Example 19. Likewise, by utilizing tris LK3phosphite as the phosphite in Example 19 there is obtained thecorresponding hexol phosphonate having a molecular weight of 1350 andhydroxyl number of 250. Also, by employing trispentaerythritolpro-pylene oxide adduct phosphite, molecular weight 450,there is obtained the corresponding nonol phosphonate having a molecularweight of 1230 and a hydroxyl number of 410. The pentol, hex-ol andnonol phosphonates are useful for preparing rigid polyurethane foams.

Unsaturated phosphon-ates can be formed by reacting an excess of allylchloride, metallyl chloride, allyl bromide, or metha-llyl bromide withtris-diethylene glycol phosphite or tris dipropylene glycol phosphite.These compounds are useful in preparing urethanes having the usesenumerated supra.

Example 35 One mole of tris diethylene glycol phosphite was refluxedwith 6 moles of allyl chloride until there was no increase in P=O bondin the infrared analysis. Volatile material was stripped off first atatmospheric pressure up to C. and then at 10 mm. and C. to recover thehis diethylene glycol allylp-hosphonate, molecular weight 298, hydroxylnumber 375, as a liquid.

Example 36 The process of Example 35 was repeated replacing the trisdiethylene glycol phosphite by one mole of tris dipropylene glycolphosphite to produce bis-dipropylene glycol allylphosphonate, molecularweight 312, and hydroxyl number 360, as a liquid.

Example 37 The process of Example 35 was repeated replacing the allylchloride by 6 moles of methallyl chloride to produce bis-diethyleneglycol methallylph-osphonate, molecular weight 354, hydroxyl number 316,as a liquid.

Example 38 The process of Example 37 was repeated but the trisdiethylene glycol phosphite was replaced, by one mole of trisdipropylene glycol phosphite to produce bis-dipropylene glycolmethallylph-osphonate, a viscous liquid having a molecular weight of 368and a hydroxyl number of 305.

The compounds prepared in Examples 3538 have the formula The diolalkenephosphonates thus produced can be polymerized, e.g., with free radicalproducing agents such as benzoyl peroxide, or reacted with di or otherpolycarb-oxylic acids to give airdrying polyesters. Alternatively, theycan be reacted with polyisocyana-tes, e.g., toluene diisocyanate, togive polyurethanes which can be further polymerized by virtue of theethylenic double bond to give products useful as coatings, castings,etc. The prodnets are either self-extinguishing or nonburning. Thedi-olalkenephosphonates can be copolymerized with other materials havingethyl-enic unsaturation, e.g., acrylates such as methyl acrylate, butylacryl-ate and methyl methacrylate, styrene, acrylon-itrile, ethylene andpropylene. They can also be used as cross-linking agents. Additionally,the polymers produced can have enhanced dyeing properties because of thepolarity introduced.

There can also be prepared neopentylene allylphosphonate, neopentylenemethallylphosphonate, pentaerythritol diallylphosphonate andpentaerythri-tol d-imethallylphosphonate. These materials have nohydroxyl groups. They are useful, however, as monomers which can becopolymerized with other materials to produce polymers of improved fireresistance and enhanced dyeing and printing characteristics. They can becopolymerized with acrylates and methacrylates such as methyl acrylate,butyl acrylate and methyl methacrylate, acrylonitrile and ethylenicallyunsaturated hydrocarbons such as styrene, ethylene, propylene andisobutylene.

These compounds can be prepared by reacting an excess of allyl chloride,allyl bromide, methallyl chloride or methallyl bromide with theappropriate phosphite.

Example 39 One mole of 2-decyloxy-5,5-dimet hyl-1,3,2-dioxaphosphorinanewas refluxed with 6 moles of allyl chloride until there was no increasein P=O bond in the infrared analysis. Volatile material was stripped 01ffirst at atmospheric pressure up to 100 C. and then at mm. and up to 150C. to distill over the 2-allyl-2-oxo-5,S-dimethyI- 1,3,2-dioxaphosphorinane as liquid followed by the decylchloride. When methallylbromide is substituted for allyl chloride, the correspondingZ-methallyl-Z-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane is produced.

Example 40 The procedure of Example 39 is repeated employing one mole of3,9-didecyloxy-2,4,8,10-tetraoxa-3,9-dipho-sphaspiro-[5,5]-undecane inplace of the dioxaphosphorinane compound. There was obtained3,9-diallyl-3,9- dioxo 2,4,8,10 tetraoxa-3,9-diphosphaspiro-[5,5]-undecane as the solid residue. This compound can also be calledpentaerythritol diallyl diphosphonate.

When methallyl bromide is substituted for allyl chloride in Example 40,the corresponding pentaerythritol diallyl diphosphonate is produced.

Example 41 The low molecular weight polymer prepared from 1 rnole ofpentaerythritol, 2 moles of triphenyl phosphite and 1.1 moles (a 0.1mole excess) of diethylene glycol (prepared according to applicationSerial No. 111,899, filed May 23, 1961) was refluxed for 5 hours with 6moles of allyl chloride (200% excess) until rearrangement was complete.Excess allyl chloride followed by B,,6'-dichlorodiethyl ether,diethylene glycol and B-hydroxyethoxyethyl chloride were removed byvacuum distillation. The residue was essentially pure pentaerythritoldiallyl diphosphonate.

In a similar manner, one mole of the linked phosphorinane prepared fromneopentylene glycol, triphenyl phosphite and diethylene glycol preparedaccording to Friedman et al. application Serial No. 56,129, filedSeptember 15, 1960, is reacted with 3 moles of allyl chloride (anexcess) to produce the neopentylene allyl phosphonate of Example 39.

Example 42 18 grams of bis-dipropylene glycol allyl phosphonate and 20.4grams of toluene diisocyanate were dissolved in a mixture of 20 grams ofCellosolve acetate (ethoxyethyl acetate) and 20 grams of toluene andrefluxed for one hour. The initial reaction was exothermic. Theresulting solution was useful for the preparation of urethane coatingsby spraying, dipping or painting. Curing was effected by atmosphericmoisture. The resultant products were hard, clear, flame-resistantcoatings, e.g., on Wood.

Example 43 62 grams of his dipropylene glycol allyl phosphonate and 34grams of toluene diisocyanate in a mixture of 40 grams of Cellosolveacetate and 40 grams of toluene were heated in the presence of 0.02 ml.of N-methylmorpholine for 6 hours. The solution became more viscous andthe product was essentially a linear polyurethane with pendant allylgroups. One gram of benzoyl peroxide was added to the cooled solution.The solution was then sprayed onto wood and metal strips, excess Solventallowed to evaporate and then the coating was cured at C. in an oven for2 hours. The product was a clear, hard, nonflammable, almost colorlesscoating.

Example 44 62 grams of his dipropylene glycol allyl phosphonate and 33grams of adipic acid were esterified in the presence of Dowex-50 cationexchange resin (sulfonated styrenedivinyl benzene copolymer) as acatalyst. The water formed was azeotroped outwith toluene. Whenesterification was complete, the ion exchange resin was removed byfiltration and the toluene solution concentrated to 50%. Brushapplication to wood and metal gave a lacquer which was cured by airdrying. The surface was clear, very hard, tough and nonflammable.

According to the present invention, there can be made numerous compoundshaving the formula where n is an integer, usually between 1 and 6, and Ris aliphatic hydrocarbon or hydrocarbon ether and R is hydrocarbon.Further examples of such compounds are given below. These compounds haveall the uses of the hydroxy containing phosphites and phosphonatespreviously set forth.

Example 45 300 grams (0.95 mole) of his dipropylene glycol hydrogenphosphite and 5 grams of triethylamine (catalyst) were treated withcooling and 44 grams (1 mole) of acetaldehyde. The reaction wasexothermic. When reaction appeared to be complete, the mixture washeated on a steam bath for one hour and then stripped in vacuum at C. toremove catalyst and excess acetaldehyde. To help facilitate removal ofthese components, nitrogen sparging was also used. There was recoveredbis dipropylene glycol a-hydroxyethane phosphonate as a liquid,molecular weight 358, and hydroxyl number 462. Other tertiary amines andbasic catalysts can be used.

There can be used an anion exchange resin as the catalyst. Thus,quaternary ammonium ion exchange resins of the Dowex and Amberlite type(quaternarized aminomethyl styrene-divinyl benzene copolymers) can beused.

Example 46 430 grams of tris dipropylene glycol phosphite (1.0 mole) and0.2 ml. of concentrated hydrochloric acid were treated with 18.0 gramsof water to produce the his dipropylene glycol hydrogen phosphite byhydrolysis. Excess strongly basic Amberlite IR-4l0 ion exchange resinwas then added followed by 50 grams (an excess) of acetaldehyde. Whenthe reaction appeared to be complete, the mixture was heated for onehour at 100 C. The catalyst was filtered off, the filtrate stripped inhigh vacuo, with a nitrogen gas stream to help remove dipropyleneglycol. The product was identical with that in Example 1.

Example 47 hyde. The reaction was exothermic and rapid. The

mixture was heated to 100 C., maintained at 100 C. for

19 one hour, the catalyst removed by filtration and the filtratestripped under vacuum to remove volatiles. The liquid product was trisdipropylene glycol bis (oc-hydroxy ethane) phosphonate.

Example 48 In a manner similar to Example 46 there was reacted 30 gramsof formaldehyde generated by the decomposition of trioxane with hisdipropyle-ne glycol hydrogen phosphite to give his dipropylene glycolhydroxymethane phosphonate, molecular weight 344, hydroxyl number 480.

In similar fashion, tris dipropylene glycol bis hydroxymethanediphosphonate was prepared from formaldehyde and tris dipropylene glycoldihyd-rogen diphosphite. The product was a liquid.

Example 49 25 grams of his dipropylene glycol a-hydroxyethanephosphonate and 65 grams of toluene diisocyanate were stirredcontinuously without external heat until a temperature of 100 C. wasreached. This temperature was maintained for one hour. The viscousmixture was cooled and allowed to remain overnight. The properties ofthe resultant prepolymer were viscosity at 25 C. about 500 cps., freeNCO content about 25%, yield 90 grams.

To 50 grams of the prepolymer there was added with agitation a mixtureof Silicone DC-199 (a polydimethylsiloxane) in an amount of 0.25 gram,0.5 gram of diethanolarnine, 0.75 gram of water, 13.0 grams of hisdipropylene glycol a-hydroxyethane phosphonate and 5.0 grams of Quadrol.The mixture was allowed to foam and became tack free in about 15minutes. The foam had a density of about 3 lb./cubic foot, and wasuseful as a rigid nonflammable 'foam.

What is claimed is:

1. A polyurethane comprising the reaction product of an organicpolyisocyanate and phosphate and thiophosphate esters of an alkaneetherpolyol having 3 to 6 hydroxyl groups and having not more than onehydroxyl group per carbon atom, said alkaneether polyol being the etherof an alkane polyol having 3 to 6 carbon atoms and 3 to 6 hydroxylgroups and a member of the group consisting of alkylene glycols having 2to 4 carbon atoms in the alkylene group and polyalkylene glycols having2 to 4 carbon atoms in the alkylene group, said esters having at least 6free hydroxyl groups and each of the oxygen atoms attached to aphosphorus atom being in turn attached to a carbon atom of alkane etherpolyol.

2. A polyurethane according to claim 1 in the form of a foam.

3. A polyurethane comprising the reaction product of (1) a phosphateester of an alkaneether polyol having 3 to 6 hydroxyl groups and havingnot more than one hydroxyl group per carbon atom, said alkaneetherpolyol being the ether of an alkane polyol having 3 to 6 carbon 20 atomsand 3 to 6 hydroxyl groups and a polyalkylene glycol having 2 to 4carbon atoms in the alkylene group, said ester having at least 6 freehydroxyl groups and each of the oxygen atoms attached to a phosphorusatom being in turn attached to a carbon atom of the alkane ether polyoland (2) an organic polyisocyanate.

4. A foamed product according to claim 3 wherein the organicpolyisocyanate is an aromatic diisocyanate.

5. A product according to claim 3 wherein the organic polyisocyanate isan aromatic diisocyanate and the phosphate ester is tris (poly-propyleneglycol ether of 1,2,6- hexanetriol) phosphate in the form of a foam.

6. A product according to claim 3 wherein the organic polyisocyanate isan aromatic diisocyanate and the phosphate ester is tris (polypropyleneglycol ether of glycerine) phosphate in the form of a foam.

7. A product according to claim 3 wherein the organic polyisocyanate isan aromatic diisocyanate and the phosphate ester is tris (polypropyleneglycol ether of pentaerythritol) phosphate in the form of a foam.

8. A polyurethane comprising the reaction product of an organicpolyisocyanate and the phosphate of -a poly alkylene glycol ether ofpentaerythritol having 2 to 4 carbon atoms in each alkylene group.

9. A polyurethane according to claim 8 wherein the organicpolyisocyanate is an aromatic diisocyanate and the polyalkylene glycolether of pentaerythritol is his polypropylene glycol pentaerythritoldiphosphate.

10. A polyurethane comprising the reaction product of an organicpolyisocyanate and tris (tetramethylcyclobutanediol) phosphate.

11. A polyurethane comprising the reaction product of an organicpolyisocyanate and a phosphate ester of a member of the group consistingof alkylene glycol having 2 to 4 carbon atoms in the alkylene group andpolyalkylene glycol ethers of a hydroxyarylalkane having 2 to 3hydroxyaryl groups attached to the alkane unit and having 2 to 4 carbonatoms in each alkylene group, said ester having 3 to 6 free hydroxylgroups.

References Cited by the Examiner UNITED STATES PATENTS 2,176,080 10/1939Katzman 260461 2,177,984 10/1939 Harris 260461 3,142,651 7/1964 Friedman2602.5

FOREIGN PATENTS 1,106,489 3/ 1961' Germany.

OTHER REFERENCES Kosolopoff: Organo-Phosphorou-s Compounds, John Wiley &Sons, NY. (1950), pp. 220-223.

LEON J. BERCOVITZ, Primary Examiner.

1. A POLYURETHANE COMPRISING THE REACTION PRODUCT OF AN ORGANICPOLYISOCYANATE AND PHOSPHATE AND THIOPHOSPHATE ESTERS OF AN ALKANEETHERPOLYOL HAVING 3 TO 6 HYDROXYL GROUPS AND HAVING NOT MORE THAN ONEHYDROXYL GROUP PER CARBON ATOM, SAID ALKANEETHER POLYOL BEING THE ETHEROF AN ALKANE POLYOL HAVING 3 TO 6 CARBON ATOMS AND 3 TO 6 HYDROXYLGROUPS AND A MEMBER OF THE GROUP CONSISTING OF ALKYLENE GLYCOLS HAVING 2TO 4 CARBON ATOMS IN THE ALKYLENE GROUP AND POLYALKYLENE GLYCOLS HAVING2 TO 4 CARBON ATOMS IN THE ALKYLENE GROUP, SAID ESTERS HAVING AT LEAST 6FREE HYDROXYL GROUPS AND EACH OF THE OXYGEN ATOMS ATTACHED TO APHOSPHORUS ATOM BEING IN TURN ATTACHED TO A CARBON ATOM OF ALKANE ETHERPOLYOL.